Polycrystalline compacts, earth-boring tools including such compacts, and methods of fabricating polycrystalline compacts

ABSTRACT

A polycrystalline compact includes diamond, cubic boron nitride, and at least one hard material, which may be aluminum nitride, gallium nitride, silicon nitride, titanium nitride, silicon carbide, titanium carbide, titanium boride, titanium diboride, and/or aluminum boride. The diamond, the cubic boron nitride, and the hard material are intermixed and interbonded to form a polycrystalline material. An earth-boring tool includes a bit body and a polycrystalline diamond compact secured to the bit body. Methods of fabricating polycrystalline compacts include forming a mixture comprising diamond, non-cubic boron nitride, and a metal or semimetal; encapsulating the mixture in a container; and subjecting the encapsulated mixture to high-pressure and high-temperature conditions to form a polycrystalline material.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. patent application Ser. No.14/090,018, filed Nov. 26, 2013, now U.S. Pat. 9,498,867, issued Nov.22, 2016, the disclosure of which is hereby incorporated herein in itsentirety by this reference.

FIELD

Embodiments of the present disclosure relate generally topolycrystalline compacts and methods of forming polycrystallinecompacts, which may be used, for example, as cutting elements forearth-boring tools.

BACKGROUND

Earth-boring tools for forming wellbores in subterranean earthformations may include a plurality of cutting elements secured to abody. For example, fixed-cutter earth-boring rotary drill bits (alsoreferred to as “drag bits”) include a plurality of cutting elementsfixedly attached to a bit body of the drill bit. Similarly, roller coneearth-boring rotary drill bits include cones mounted on bearing pinsextending from legs of a bit body such that each cone is capable ofrotating about the bearing pin on which the cone is mounted. A pluralityof cutting elements may be mounted to each cone of the drill bit.

The cutting elements used in such earth-boring tools often includepolycrystalline diamond cutters (often referred to as “PDCs”), which arecutting elements that include a polycrystalline diamond (PCD) material.Such polycrystalline diamond cutting elements are formed by sinteringand bonding together relatively small diamond grains or crystals underconditions of high temperature and high pressure in the presence of acatalyst (such as cobalt, iron, nickel, or alloys and mixtures thereof)to form a layer of polycrystalline diamond material on a cutting elementsubstrate. These processes are often referred to as “high-pressure,high-temperature” (or “HPHT”) processes. The cutting element substratemay be a cermet material (i.e., a ceramic-metal composite material) suchas cobalt-cemented tungsten carbide. In such instances, the cobalt orother catalyst material in the cutting element substrate may be drawninto the diamond grains or crystals during sintering and serve as acatalyst material for forming a diamond table from the diamond grains orcrystals. In other methods, powdered catalyst material may be mixed withthe diamond grains or crystals prior to sintering the grains or crystalstogether in an HPHT process.

Cobalt, which is commonly used in sintering processes to form PCDmaterial, melts at about 1,495° C. The melting temperature may bereduced by alloying cobalt with carbon or another element, so HPHTsintering of cobalt-containing bodies may be performed at temperaturesabove about 1,450° C.

Upon formation of a diamond table using an HPHT process, catalystmaterial may remain in interstitial spaces between the grains orcrystals of diamond in the resulting polycrystalline diamond table. Thepresence of the catalyst material in the diamond table may contribute tothermal damage in the diamond table when the cutting element is heatedduring use, which heating is caused by friction at the contact pointbetween the cutting element and the formation. Polycrystalline diamondcutting elements in which the catalyst material remains in the diamondtable are generally thermally stable up to temperatures of about 750°C., although internal stress within the polycrystalline diamond tablemay begin to develop at temperatures exceeding about 350° C. Thisinternal stress is at least partially due to differences in the rates ofthermal expansion between the diamond table and the cutting elementsubstrate to which it is bonded. For example, diamond has a linearthermal expansion coefficient (TEC) at 25° C. of about 0.8·10⁻⁶K⁻¹,whereas cobalt has a TEC at 25° C. of about 12·10⁻⁶K⁻¹. At 800° C.,diamond has a TEC of about 4.5·10⁻⁶K⁻¹, and cobalt has a TEC of about17.0·10⁻⁶K⁻¹. At temperatures of about 750° C. and above, stresseswithin the diamond table may increase significantly due to differencesin the coefficients of thermal expansion of the diamond material and thecatalyst material within the diamond table itself. For example, cracksmay form and propagate within a diamond table including cobalt,eventually leading to deterioration of the diamond table andineffectiveness of the cutting element. Besides being a source ofthermomechanically initiated stresses, catalyst materials used to formpolycrystalline diamond can also catalyze the phase transformation ofdiamond into graphite (commonly referred to as “reversegraphitization”), which contributes to degradation of diamond tables.

To reduce the problems associated with catalyst material (e.g.,different rates of thermal expansion in polycrystalline-diamond cuttingelements and reverse graphitization), so-called “thermally stable”polycrystalline diamond cutting elements have been developed. Such athermally stable polycrystalline-diamond cutting element may be formedby leaching the catalyst material (e.g., cobalt) out from interstitialspaces between the diamond grains in the diamond table using, forexample, an acid. All of the catalyst material may be removed from thediamond table, or only a portion may be removed. Thermally stablepolycrystalline diamond cutting elements in which substantially allcatalyst material has been leached from the diamond table have beenreported to be thermally stable up to temperatures of about 1,200° C. Ithas also been reported, however, that fully leached diamond tables arerelatively more brittle and vulnerable to shear, compressive, andtensile stresses than are non-leached diamond tables. In an effort toprovide cutting elements having diamond tables that are more thermallystable relative to non-leached diamond tables, but that are alsorelatively less brittle and vulnerable to shear, compressive, andtensile stresses relative to fully leached diamond tables, cuttingelements have been provided that include a diamond table in which only aportion of the catalyst material has been leached from the diamondtable.

BRIEF SUMMARY

In some embodiments, a polycrystalline compact includes diamond grains,cubic boron nitride grains, and grains of an additional nitride, carbonor boride. The additional nitride, carbide, or boride may be aluminumnitride, gallium nitride, silicon nitride, titanium nitride, siliconcarbide, titanium carbide, titanium boride, titanium diboride, and/oraluminum boride. The diamond grains, the cubic boron nitride grains, andthe grains of the additional nitride, carbide, or boride are intermixedand interbonded to form a polycrystalline material.

An earth-boring tool includes a bit body and a polycrystalline diamondcompact secured to the bit body. The polycrystalline diamond compactincludes diamond grains, cubic boron nitride grains, and grains of anadditional nitride, carbide, or boride. The additional nitride, carbide,or boride may be aluminum nitride, gallium nitride, silicon nitride,titanium nitride, silicon carbide, titanium carbide, titanium boride,titanium diboride, and/or aluminum boride. The diamond grains, the cubicboron nitride grains, and the grains of the additional nitride, carbide,or boride are intermixed and interbonded to form a polycrystallinematerial.

In certain embodiments, a method of fabricating a polycrystallinecompact includes forming a mixture comprising diamond grains, non-cubicboron nitride grains, and a metal or semimetal; encapsulating themixture in a container; and subjecting the encapsulated mixture to apressure of at least 5.0 GPa and a temperature of at least 1,100° C. toform a polycrystalline material from the mixture. The polycrystallinematerial comprises the diamond grains, cubic boron nitride grains formedfrom the non-cubic boron nitride grains, and grains of an additionalnitride, carbide, or boride selected from the group consisting ofaluminum nitride, gallium nitride, silicon nitride, titanium nitride,silicon carbide, titanium carbide, titanium boride, titanium diboride,and aluminum boride. The diamond grains, the cubic boron nitride grains,and the grains of the additional nitride, carbide, or boride areintermixed and interbonded within the polycrystalline material.

BRIEF DESCRIPTION OF THE DRAWINGS

While the specification concludes with claims particularly pointing outand distinctly claiming what are regarded as embodiments of the presentdisclosure, various features and advantages of embodiments of thedisclosure may be more readily ascertained from the followingdescription of example embodiments when read in conjunction with theaccompanying drawings, in which:

FIG. 1 is a simplified illustration showing a mixture for use in forminga polycrystalline compact according to the present disclosure;

FIG. 2 is a simplified illustration showing the mixture of FIG. 1 afterHPHT sintering;

FIG. 3 is a simplified illustration showing the mixture of FIG. 1 in acanister for HPHT sintering;

FIG. 4 shows a partial cutaway illustration of a polycrystalline compactaccording to the present disclosure;

FIG. 5 illustrates a fixed-cutter type earth-boring rotary drill bitthat includes a plurality of cutting elements, such as thepolycrystalline compact shown in FIG. 4;

FIG. 6 illustrates X-ray diffraction (XRD) analysis of a polycrystallinecompact according to the present disclosure;

FIGS. 7 and 8 are scanning electron microscope (SEM) images of afractured portion of a polycrystalline compact at 5,000× and 20,000×magnification, respectively; and

FIG. 9 is a photograph of a fractured portion of a polycrystallinecompact showing areas tested by energy-dispersive X-ray spectroscopy(EDS) to measure elemental composition.

DETAILED DESCRIPTION

The illustrations presented herein are not meant to be actual views ofany particular material, apparatus, system, or method, but are merelyidealized representations employed to describe certain embodiments. Forclarity in description, various features and elements common among theembodiments may be referenced with the same or similar referencenumerals.

As used herein, the term “drill bit” means and includes any type of bitor tool used for drilling during the formation or enlargement of awellbore and includes, for example, rotary drill bits, percussion bits,core bits, eccentric bits, bicenter bits, reamers, expandable reamers,mills, drag bits, roller cone bits, hybrid bits, and other drilling bitsand tools known in the art.

The term “polycrystalline material” means and includes any materialcomprising a plurality of grains (i.e., crystals) of the material thatare bonded directly together by inter-granular bonds. The crystalstructures of the individual grains of the material may be randomlyoriented in space within the polycrystalline material.

As used herein, the term “inter-granular bond” means and includes anydirect atomic bond (e.g., ionic, covalent, metallic, etc.) between atomsin adjacent grains of material.

As used herein, the term “grain size” means and includes a geometricmean diameter of grains measured from a two-dimensional section througha bulk polycrystalline material. The geometric mean diameter of grainsmay be determined using techniques known in the art, such as those setforth in Ervin E. Underwood, QUANTITATIVE STEREOLOGY, 103-105(Addison-Wesley Publishing Company, Inc., 1970), the disclosure of whichis incorporated herein in its entirety by this reference.

As used herein, the term “particle size” means and includes a largestlinear dimension of a particle (sometimes referred to as “diameter”). Asused herein, “average particle size” refers to the number averageparticle size based on the largest linear dimension of a group ofparticles. Particle size, including average, maximum, and minimumparticle sizes, may be determined by an appropriate method of sizingparticles such as, for example, static or dynamic light scattering (SLSor DLS) using a laser light source, physical classification such asscreening, or any other appropriate method. Accurate measurement ofparticle sizes may depend on the size range of the particles to bemeasured.

FIG. 1 is a simplified illustration showing a mixture 102 for use informing a polycrystalline compact. The mixture 102 includes diamondgrains 104, boron nitride grains 106, and a metal or semimetal 108.

The diamond grains 104 may be any suitable type and form of diamond,including natural and synthetic diamonds. The diamond grains 104 mayinclude, for example, micron-size diamond having an average particlesize from about 1 μm to about 40 μm, such as from about 5 μm to about 30μm, or from about 7 μm to about 10 μm. The diamond grains 104 may benatural or synthetic, and may be formed and/or classified by anyappropriate methods.

The diamond grains 104 may be monodisperse (i.e., all particles are ofsubstantially the same size with little variation) or polydisperse(i.e., the particles have a range or distribution of sizes). Diamondgrains 104 of different average particle size, monodisperse orpolydisperse, or both, may be used, and the particle size distributionof the micron diamonds may be unimodal, bimodal, or multi-modal. In someembodiments, the diamond grains 104 may be or include nanometer-sizediamond having an average particle size from about 50 nm to about 1 μm.Diamond grains 104 may be used as received, or may be sorted and cleanedby various methods to remove contaminants and non-diamond carbon phasesthat may be present, such as residues of amorphous carbon or graphite.The diamond grains 104 may comprise, for example, from about 80% toabout 95% by weight of the mixture 102.

The boron nitride grains 106 may be in any selected form, such as in anamorphous or crystalline form. For example, the boron nitride grains 106may be in a non-cubic form. The boron nitride grains 106 may be in awurtzitic crystalline form, a form of boron nitride having a hexagonalstructure, which may be referred to as “w-BN.” The boron nitride grains106 may include, for example, submicron and/or micron-size boron nitridehaving an average particle size from about 0.1 μm to about 40 μm, suchas from about 5 μm to about 30 μm, or from about 7 μm to about 10 μm.The boron nitride grains 106 may be selected to be approximately thesame size as the diamond grains 104. The boron nitride grains 106 maycomprise, for example, from about 5% to about 30% by weight of themixture 102, such as from about 10% to about 20% by weight.

The metal or semimetal 108 may be, for example, aluminum, gallium,silicon, or titanium, or combinations, oxides, or alloys thereof. Forexample, if the metal or semimetal 108 includes aluminum, the aluminummay include a coating of aluminum oxide. The metal or semimetal 108 maybe selected to be substantially free of cobalt, iron, or nickel. Cobalt,iron, and nickel, though commonly used in PDC manufacture, tend to causeinstabilities at high temperatures encountered in drilling operations.The metal or semimetal 108 may be selected to have a melting temperatureunder pressure below about 1,200° C., such as below about 1,000° C., oreven below about 800° C. The metal or semimetal 108 may be in aparticulate form, such as a powder, having an average particle size inthe micron or nanometer range. For example, the metal or semimetal 108may be in the form of particles have an average particle size betweenabout 50 nm and about 1 μm, such as between about 100 nm and about 500nm. The metal or semimetal 108 may comprise, for example, from about 1%to about 10% by weight of the mixture 102, such as from about 2% toabout 5% by weight.

The mixture 102 may be processed in preparation for subjecting themixture 102 to an HPHT sintering process. For example, a slurry may beprepared that includes the mixture 102 by adding one or more ofmethanol, ethanol, isopropanol, acetone, hexane, water, or any otherappropriate liquid to the mixture 102. The slurry may be used to improvethe homogeneity of the mixture 102 (i.e., the uniformity of thedistribution of the different components of the mixture 102). Ultrasonicenergy optionally may be imparted to the slurry to further improve thehomogeneity of the mixture 102. In some embodiments, the mixture 102 maybe mechanically mixed without any added liquid. The mixture 102 may bemixed in an apparatus for grinding or crushing. For example, the mixture102 may be mixed with a mortar and pestle, with a stir bar in a flask,or with a production-scale mechanical mixing apparatus.

To form a compact 116 (see FIG. 2), the diamond grains 104, the boronnitride grains 106, and the metal or semimetal 108 may be placed in acontainer 110 before, during, or after forming the mixture 102. Forexample, the container 110 may be a piston-cylinder chamber, a pair ofBridgeman anvils, a belt apparatus, a multi-anvil apparatus, or atoroid-type high-pressure device. Such devices are described in, forexample, L. G. Khvostantsev et al., “Toroid Type High-Pressure Device:History and Prospects,” High Pressure Research, vol. 24, No. 3, pp.371-83 (September 2004), the entire contents of which are incorporatedherein by this reference.

The mixture 102 may be subjected to HPHT conditions (e.g., sintered) toform a compact 116 having inter-granular bonds between the diamondgrains 104 and to form grains of an additional nitride, boride, orcarbide 114, as shown in FIG. 2. HPHT conditions may also cause thecompaction of the materials and the conversion of at least a portion ofthe boron nitride grains 106 from a non-cubic form to cubic boronnitride grains 112. The grains of additional nitride, boride, or carbide114 and/or the cubic boron nitride grains 112 may help bind the diamondgrains 104 together, and may fill voids between the diamond grains 104.Thus, the compact 116 may have a higher density than the mixture 102before sintering.

In some embodiments, the mixture 102 may be subjected to a pressure fromabout 5.0 GPa to about 10.0 GPa, such as from 7.0 GPa to about 9.0 GPa,or a pressure of at least about 7.5 GPa. The mixture 102 may besubjected to a temperature from about 1,100° C. to about 1,900° C., suchas a temperature from about 1,200° C. to about 1,800° C. or atemperature of at least about 1,400° C. The time during which the HPHTconditions are maintained may vary based on the temperature, pressure,volume and composition of material, or other factors. In someembodiments, the HPHT conditions may be maintained for a time periodfrom about 1 second to about 5 minutes. For example, HPHT conditions maybe maintained for a time period from about 5 seconds to about 1 minute.The pressure, temperature, and time of HPHT processing may affect thefinal density and other properties of the compact 116.

In some embodiments, the metal or semimetal 108 may melt before thefinal temperature of the HPHT sintering process is reached, and may meltbefore the graphitization of diamond occurs. The metal or semimetal 108in its liquid state may wet the surface of the diamond grains 104 andparticles of boron nitride grains 106. The metal or semimetal 108 mayfacilitate efficient densification of the compact 116. As a result, agraphite phase, which causes weakening of the compact 116, may not beformed under these conditions. The metal or semimetal 108 may flowwithin the mixture 102, allowing the diamond grains 104 and/or the boronnitride grains 106 to rearrange relative to one another, increasing thepacking fraction and the density of the compact 116 to be formed. Forexample, aluminum melts at a temperature of about 660° C., silicon meltsat about 1,412° C., and titanium melts at about 1,668° C. Gallium is aliquid at room temperature, so if gallium is used, it may be liquidduring formation of the mixture 102. Thus, the metal or semimetal 108may be in a liquid state during at least part of time while the mixture102 is brought to HPHT conditions.

During HPHT processing, the grains of additional nitride, boride, orcarbide 114 may be formed by the reaction of nitrogen in the boronnitride grains 106 with the metal or semimetal 108 in the mixture 102.For example, if the metal or semimetal 108 is aluminum, aluminumnitride, cubic boron nitride, and boron may form according to thefollowing reaction:2w−BN+Al→c−BN+AlN+B.Thus, a portion of the nitrogen and boron in the boron nitride may bindto the aluminum. Boron can also react chemically with the diamond toform a carbide such as B₄C. When an aluminum-titanium powder mixture oralloy is used in the process of HPHT sintering with diamond, aluminumnitride (AlN), titanium diboride (TiB₂), and titanium carbide (TiC) maybe formed. Metals, semi-metals, and their mixtures and alloys arespecially selected in order to yield, after the HPHT process, compactscontaining diamond and nitrides, borides and/or carbides. The compactsmay be substantially free of materials having melting temperatures lowerthan about 2,000° C. Such compacts may have relatively high mechanicalstrength in comparison with conventional compacts, and may have a TECnearer the TEC of diamond at temperatures in a range from about 700° C.to about 1,000° C. In some embodiments, an unreacted portion of themetal or semimetal 108 may remain as elemental metal or semimetal, mayphysically flow from the compact 116, and may be removed. Furthermore,remaining portions of the metal or semimetal 108 may be removed bychemical means, such as leaching, etc.

In some embodiments, the container 110 may be a canister used for HPHTprocessing to form polycrystalline compacts, such as a container 310, asshown in FIG. 3. The container 310 may include one or more generallycup-shaped members, such as a cup-shaped member 312, a cup-shaped member314, and a cup-shaped member 316, which may be assembled and swagedand/or welded together to form the container 310. The mixture 102 and anoptional cutting element substrate 320 may be disposed within the innercup-shaped member 314, which has a circular end wall and a generallycylindrical lateral side wall extending perpendicularly from thecircular end wall, such that the inner cup-shaped member 314 isgenerally cylindrical and includes a first closed end and a second,opposite open end.

After providing the mixture 102 and, if present, the cutting elementsubstrate 320, within the container 310, the assembly may optionally besubjected to a cold pressing process to compact the powder mixture 102to form an unsintered preform 300. The unsintered preform 300 may thenbe subjected to HPHT conditions as described above.

The processes disclosed herein may be used to form polycrystallinecompacts of cutting elements. The use of a metal or semimetal (e.g.,aluminum, silicon, etc.) and wurtzitic boron nitride as additives todiamond crystals in HPHT sintering processes may provide a new class ofsuperhard polycrystalline materials having advanced physical andmechanical properties and improved work efficiency in cuttingapplications.

As shown in FIG. 4, a cutting element 400 has a generally cylindrical,or disk-shaped, configuration. An exposed, major surface of a hardpolycrystalline material 410, which major surface may or may not beplanar as depicted, defines a cutting face 402 of the cutting element400. A lateral side surface 404 of the hard polycrystalline material 410extends from the cutting face 402 of the hard polycrystalline material410 to the cutting element substrate 412 on a lateral side of thecutting element 400. While a planar interface is depicted between thehard polycrystalline material 410 and cutting element substrate 412,non-planar interfaces of varying configurations and complexity areconventional and within the scope of the present disclosure. In theembodiment shown in FIG. 4, the hard polycrystalline material 410 maycomprise a generally planar table that extends to and is exposed at thelateral side surface 404 of the cutting element 400. For example, alower portion of the lateral side surface 404 of the hardpolycrystalline material 410 may have a generally cylindrical shape, andan upper portion of a lateral side surface 404 of the polycrystallinecompact adjacent the cutting face 402 may have an angled, frustoconicalshape and may define or include, for example, one or more chamfersurfaces 408 of the cutting element 400.

The hard polycrystalline material 410 may include diamond grains 104,cubic boron nitride grains 112, and grains of additional nitride,boride, or carbide 114 (see FIG. 2), as described above. The diamondgrains 104 may be monodisperse or polydisperse. The diamond grains 104may be micron-size diamond having a grain size from about 1 μm to about40 μm, such as from about 5 μm to about 30 μm, or from about 7 μm toabout 10 μm. In some embodiments, the diamond grains 104 may be orinclude nanometer-size diamond having a grain size from about 50 nm toabout 1 μm. Diamond grains 104 of different average particle size,monodisperse or polydisperse, or both, may be present in the hardpolycrystalline material 410, and the particle size distribution of themicron diamonds may be unimodal, bimodal, or multi-modal. The diamondgrains 104 may comprise, for example, from about 70% to about 90% byweight of the hard polycrystalline material 410.

The cubic boron nitride grains 112 may include, for example, micron-sizecubic boron nitride having a grain size from about 1 μm to about 40 μm,such as from about 5 μm to about 30 μm, or from about 7 μm to about 10μm. The cubic boron nitride grains 112 may be approximately the samesize as the diamond grains 104 or may be of a different size than thediamond grains 104. The cubic boron nitride grains 112 may comprise, forexample, from about 5% to about 30% by weight of the hardpolycrystalline material 410, such as from about 10% to about 15% byweight.

Overall, the hard polycrystalline material 410 may include from about 65atomic percent to about 95 atomic percent carbon, such as from about 70atomic percent to about 90 atomic percent carbon, or from about 75atomic percent to about 85 atomic percent carbon. The hardpolycrystalline material 410 may include from about 3 atomic percent toabout 15 atomic percent boron, such as from about 5 atomic percent toabout 10 atomic percent boron, or from about 8 atomic percent to about12 atomic percent boron. The hard polycrystalline material 410 mayinclude from about 3 atomic percent to about 15 atomic percent nitrogen,such as from about 5 atomic percent to about 10 atomic percent nitrogen,or from about 8 atomic percent to about 12 atomic percent nitrogen. Thehard polycrystalline material 410 may include from about 0.05 atomicpercent to about 5.0 atomic percent aluminum, gallium, silicon, ortitanium, such as from about 0.1 atomic percent to about 2.5 atomicpercent, or from about 0.25 atomic percent to about 1.0 atomic percent.

The grains of the additional nitride, boride, or carbide 114 may be, forexample, aluminum nitride, gallium nitride, silicon nitride, titaniumnitride, silicon carbide, titanium carbide, titanium boride, titaniumdiboride, or aluminum boride, or combinations thereof. The grains of theadditional nitride, boride, or carbide 114 may have a linear TEC of lessthan about 5.0·10⁻⁶K⁻¹. The grains of the additional nitride, boride, orcarbide 114 may comprise, for example, aluminum nitride, which has alinear TEC of about 4.6·10⁻⁶K⁻¹. The hard polycrystalline material 410may be substantially free of materials having a linear TEC of greaterthan about 5.0·10⁻⁶K⁻¹. For example, the hard polycrystalline material410 may be substantially free of any metal phase comprising cobalt,iron, nickel, or alloys thereof.

The hard polycrystalline material 410 may have a density near thedensity of diamond (3.52 g/cm³). For example, the hard polycrystallinematerial 410 may have a density of at least about 3.30 g/cm³, at leastabout 3.40 g/cm³, or even at least about 3.45 g/cm³. The Young's modulusof the hard polycrystalline material 410 may also be comparable todiamond. In some embodiments, the Young's modulus of the hardpolycrystalline material 410 may be at least about 700 GPa, at leastabout 800 GPa, or even at least about 900 GPa.

Embodiments of cutting elements and polycrystalline materials (e.g.,compacts) of the invention, such as the cutting element 400 and the hardpolycrystalline material 410 described with reference to FIG. 4, may beformed and secured to earth-boring tools for use in forming wellbores insubterranean formations. As a non-limiting example, FIG. 5 illustrates afixed-cutter earth-boring rotary drill bit 500 that includes a pluralityof cutting elements 400 as previously described herein. The rotary drillbit 500 includes a bit body 502, and the cutting elements 400 aresecured to the bit body 502. The cutting elements 400 may be brazed (orotherwise secured) within pockets 504 formed in the outer surface ofeach of a plurality of blades 506 of the bit body 502.

Cutting elements and polycrystalline compacts as described herein may besecured to and used on other types of earth-boring tools, including, forexample, roller cone drill bits, percussion bits, core bits, eccentricbits, bicenter bits, reamers, expandable reamers, mills, hybrid bits,and other drilling bits and tools known in the art.

EXAMPLE

A mixture was prepared by mixing 85% by weight of diamond grains (e.g.,grit) having an average particle size of 7 μm to 10 μm with 12% byweight of wurtzitic boron nitride grains (w-BN) having an averageparticle size of 1 μm to 3 μm and 3% by weight of aluminum powder havingan average particle size of about 1 μm in ethanol. The mixture wasplaced in a container in an ultrasonic bath, and was subjected toultrasonic energy for 30 minutes. The container was then removed fromthe bath, and the ethanol was evaporated. The dried mixture wastransferred into a toroid high-pressure device, as described in,Khvostantsev et al., supra. The dried mixture was sintered at atemperature of 1,500° C. under a pressure of 8 GPa applied for 5 secondsto 30 seconds. The chamber of the toroid-type high-pressure device wasthen quenched to ambient conditions. This process yieldedpolycrystalline compact samples in the form of disks approximately 4-mmdiameter and 3-mm thick.

A sample of a polycrystalline compact sintered for 7 seconds at 1,500°C. under a pressure of 8 GPa was split lengthwise. X-ray diffraction(XRD) analysis was performed on the resulting surface, and the spectrumis shown in FIG. 6. The XRD data indicate the presence of diamond,aluminum nitride (AlN), and cubic boron nitride (c-BN) in the PDC. Thepeaks associated with w-BN do not appear in the XRD spectrum of thesintered sample. Thus, the AN and c-BN appear to have been formed duringthe sintering process from the Al and the w-BN.

The exposed surface of the split polycrystalline compact was examinedunder a scanning electron microscope (SEM). Images obtained at 5,000×and 20,000× magnification are shown in FIGS. 7 and 8, respectively. TheSEM images appear to show crystals of the c-BN and the AlN well bondedto diamond particle surfaces. Thus, adding aluminum to w-BN appears topromote the bonding of interfaces in the polycrystalline compacts. Inthe presence of aluminum at a pressure of 8.0 GPa, diamond particlesappear to form bonds with the other phases of material present andbetween each other. Without being bound to any particular theory, thisphenomenon may be due to liquid aluminum being a medium through whichcarbon atoms may be transferred.

The exposed surface of the split polycrystalline compact was subjectedto energy-dispersive X-ray spectroscopy (EDS) over three areas of thesurface to measure elemental composition. The three areas tested areshown in FIG. 9 as Areas 1, 2, and 3. The elemental compositionsdetected are shown in Table 1 below.

TABLE 1 Elemental composition of polycrystalline compact (atomic %) B CN Al Area 1 10.56% 78.48% 10.48% 0.49% Area 2 10.11% 78.43% 10.92% 0.54%Area 3 10.28% 78.02% 11.56% 0.44%Based on the EDS analysis, the polycrystalline compact appears to haveapproximately uniform chemical composition, with little variation acrossthe compact.

Three of the polycrystalline compacts were tested to determine some oftheir physical properties. In particular, sample 1 was sintered for 30seconds at 1,500° C., sample 2 was sintered for 30 seconds at 1,500° C.,followed by sintering for 5 seconds at 1,700° C., and sample 3 wassintered for 30 seconds at 1,500° C., followed by sintering for 7seconds at 1,700° C. The samples tested to determine their density,Young's modulus, and cutting performance. Young's modulus was measuredby sound propagation. Cutting performance was measured by securing thepolycrystalline compacts in a lathe and cutting hard alloy rodsconsisting of 85% tungsten carbide and 15% cobalt. The mass of the rodsremoved before the polycrystalline compacts failed was measured. Thismass indicates relative performance of the polycrystalline compacts, butis not directly comparable to other methods without standardization. Theresults of the tests are shown in Table 2. The density and Young'smodulus of diamond are also shown in Table 2 for reference.

TABLE 2 Physical properties of polycrystalline compacts Sin- CuttingSintering tering Sin- performance temper- pres- tering Den- Young's (gof hard ature sure time sity modulus alloy Sample (° C.) (GPa) (sec)(g/cm³) (GPa) removed) 1 1,500 8.0 30 3.41 785 2.7 2 1,500, 1,700 8.030, 5 3.43 885 12.2 3 1,500, 1,700 8.0 30, 7 3.45 970 11.5 Dia- 3.52900-1250 mond

Additional non-limiting example embodiments of the disclosure aredescribed below.

Embodiment 1: A polycrystalline compact comprising diamond grains, cubicboron nitride grains, and grains of an additional nitride, carbon orboride. The additional nitride, carbide, or boride is selected from thegroup consisting of aluminum nitride, gallium nitride, silicon nitride,titanium nitride, silicon carbide, titanium carbide, titanium boride,titanium diboride, and aluminum boride. The diamond grains, the cubicboron nitride grains, and the grains of the additional nitride, carbide,or boride are intermixed and interbonded to form a polycrystallinematerial.

Embodiment 2: The polycrystalline compact of Embodiment 1, wherein thepolycrystalline compact has a density of about 3.40 g/cm³ or greater.

Embodiment 3: The polycrystalline compact of Embodiment 1 or Embodiment2, wherein the polycrystalline compact has a Young's modulus of about750 GPa or greater.

Embodiment 4: The polycrystalline compact of any of Embodiments 1through 3, wherein the diamond grains consist of diamond grains having agrain size from about 1 μm to about 40 μm.

Embodiment 5: The polycrystalline compact of any of Embodiments 1through 4, wherein the polycrystalline compact comprises from about 70atomic percent to about 90 atomic percent carbon.

Embodiment 6: The polycrystalline compact of any of Embodiments 1through 5, wherein the polycrystalline compact comprises from about 5atomic percent to about 15 atomic percent boron.

Embodiment 7: The polycrystalline compact of any of Embodiments 1through 6, wherein the polycrystalline compact comprises from about 5atomic percent to about 15 atomic percent nitrogen.

Embodiment 8: The polycrystalline compact of any of Embodiments 1through 6, wherein the polycrystalline compact comprises from about 0.1atomic percent to about 5.0 atomic percent of an element selected fromthe group consisting of aluminum, gallium, silicon, and titanium.

Embodiment 9: The polycrystalline compact of any of Embodiments 1through 8, wherein the grains of the additional nitride, carbide, orboride comprise aluminum nitride grains.

Embodiment 10: The polycrystalline compact of any of Embodiments 1through 9, wherein the polycrystalline compact is substantially free ofcobalt, nickel, and iron.

Embodiment 11: An earth-boring tool comprising a bit body and apolycrystalline diamond compact secured to the bit body. Thepolycrystalline diamond compact comprises diamond grains, cubic boronnitride grains, and grains of an additional nitride, carbide, or boride.The additional nitride, carbide, or boride is selected from the groupconsisting of aluminum nitride, gallium nitride, silicon nitride, indiumnitride, and thallium titanium nitride, silicon carbide, titaniumcarbide, titanium boride, titanium diboride, and aluminum boride. Thediamond grains, the cubic boron nitride grains, and the grains of theadditional nitride, carbide, or boride are intermixed and interbonded toform a polycrystalline material.

Embodiment 12: A method of fabricating a polycrystalline compactcomprising forming a mixture comprising diamond grains, non-cubic boronnitride grains, and a metal or semimetal; encapsulating the mixture in acontainer; and subjecting the encapsulated mixture to a pressure of atleast 5.0 GPa and a temperature of at least 1,100° C. to form apolycrystalline material from the mixture. The polycrystalline materialcomprises the diamond grains, cubic boron nitride grains formed from thenon-cubic boron nitride grains, and grains of an additional nitride,carbide, or boride selected from the group consisting of aluminumnitride, gallium nitride, silicon nitride, titanium nitride, siliconcarbide, titanium carbide, titanium boride, titanium diboride, andaluminum boride. The diamond grains, the cubic boron nitride grains, andthe grains of the additional nitride, carbide, or boride are intermixedand interbonded within the polycrystalline material.

Embodiment 13: The method of Embodiment 12, wherein forming the mixturecomprising diamond grains, non-cubic boron nitride grains, and the metalor semimetal comprises mixing diamond grains with wurtzitic boronnitride and a metal or semimetal powder.

Embodiment 14: The method of Embodiment 12 or Embodiment 13, whereinforming the mixture comprising diamond grains, non-cubic boron nitridegrains, and the metal or semimetal comprises mixing the diamond grains,the non-cubic boron nitride grains, and the metal or semimetal with asolvent.

Embodiment 15: The method of Embodiment 14, further comprisingsubjecting the diamond grains, the non-cubic boron nitride grains, themetal or semimetal, and the solvent to ultrasonic energy.

Embodiment 16: The method of Embodiment 14 or Embodiment 15, furthercomprising evaporating the solvent.

Embodiment 17: The method of any of Embodiments 12 through 16, whereinsubjecting the encapsulated mixture to the pressure of at least 5.0 GPaand the temperature of at least 1,100° C. comprises converting at leasta portion of the boron nitride of the non-cubic boron nitride grainsfrom a wurtzitic phase to a cubic phase.

Embodiment 18: The method of any of Embodiments 12 through 17, whereinforming the mixture comprising diamond grains, non-cubic boron nitridegrains, and the metal or semimetal comprises mixing diamond grains withnon-cubic boron nitride grains and an aluminum powder.

Embodiment 19: The method of any of Embodiments 12 through 18, whereinsubjecting the encapsulated mixture to the pressure of at least 5.0 GPaand the temperature of at least 1,100° C. comprises maintaining theencapsulated mixture at the pressure of at least 5.0 GPa and thetemperature of at least 1,100° C. for a period of time from about 1second to about 5 minutes.

Embodiment 20: The method of any of Embodiments 12 through 19, whereinforming the mixture comprising diamond grains, non-cubic boron nitridegrains, and the metal or semimetal comprises grinding at least one ofthe diamond grains, the non-cubic boron nitride grains, and the metal orsemimetal.

Embodiment 21: The method of any of Embodiments 12 through 20, whereinforming the mixture comprising diamond grains, non-cubic boron nitridegrains, and the metal or semimetal comprises mixing metal or semimetalparticles having an average particle size from about 50 nm to about 50μm with the diamond grains and the non-cubic boron nitride grains.

Embodiment 22: The method of any of Embodiments 12 through 21, whereinforming the mixture comprising diamond grains, non-cubic boron nitridegrains, and the metal or semimetal comprises mixing diamond grainshaving an average particle size from about 50 nm to about 40 μm with themetal or semimetal and the non-cubic boron nitride grains.

Embodiment 23: The method of any of Embodiments 12 through 22, whereinforming the mixture comprising diamond grains, non-cubic boron nitridegrains, and the metal or semimetal comprises mixing non-cubic boronnitride grains having an average particle size from about 1 μm to about40 μm with the diamond grains and the metal or semimetal.

Embodiment 24: The method of any of Embodiments 12 through 23, whereinsubjecting the encapsulated mixture to the pressure of at least 5.0 GPaand the temperature of at least 1,100° C. comprises subjecting theencapsulated mixture to a pressure of at least about 7.5 GPa.

Embodiment 25: The method of any of Embodiments 12 through 24, whereinsubjecting the encapsulated mixture to the pressure of at least 5.0 GPaand the temperature of at least 1,100° C. comprises subjecting theencapsulated mixture to a temperature of at least about 1,400° C.

While the present invention has been described herein with respect tocertain illustrated embodiments, those of ordinary skill in the art willrecognize and appreciate that it is not so limited. Rather, manyadditions, deletions, and modifications to the illustrated embodimentsmay be made without departing from the scope of the invention ashereinafter claimed, including legal equivalents thereof. In addition,features from one embodiment may be combined with features of anotherembodiment while still being encompassed within the scope of theinvention as contemplated by the inventors. Further, embodiments of thedisclosure have utility with different and various bit profiles as wellas cutting element types and configurations.

What is claimed is:
 1. A polycrystalline compact, comprising: diamond;cubic boron nitride; and at least one hard material selected from thegroup consisting of aluminum nitride, gallium nitride, silicon nitride,titanium nitride, silicon carbide, titanium carbide, titanium boride,titanium diboride, and aluminum boride; wherein the diamond, the cubicboron nitride, and the hard material are intermixed and interbonded toform a polycrystalline material, and wherein the polycrystalline compactat least one of comprises from about 3 atomic percent to about 15 atomicpercent boron or has a density of at least about 3.30 g/cm³; and whereinthe polycrystalline compact comprises at least one composition selectedfrom the group consisting of: from about 65 atomic percent to about 95atomic percent carbon; from about 5 atomic percent to about 10 atomicpercent boron; from about 3 atomic percent to about 15 atomic percentnitrogen; and from about 0.05 atomic percent to about 5.0 atomic percentof an element selected from the group consisting of aluminum, gallium,silicon, and titanium.
 2. The polycrystalline compact of claim 1,wherein the polycrystalline compact has a density of at least about 3.40g/cm³.
 3. The polycrystalline compact of claim 1, wherein thepolycrystalline compact comprises from about 65 atomic percent to about95 atomic percent carbon.
 4. The polycrystalline compact of claim 1,wherein the polycrystalline compact comprises from about 5 atomicpercent to about 10 atomic percent boron.
 5. The polycrystalline compactof claim 1, wherein the polycrystalline compact comprises from about 3atomic percent to about 15 atomic percent nitrogen.
 6. Thepolycrystalline compact of claim 1, wherein the polycrystalline compactcomprises from about 0.05 atomic percent to about 5.0 atomic percent ofan element selected from the group consisting of aluminum, gallium,silicon, and titanium.
 7. The polycrystalline compact of claim 1,wherein the at least one hard material selected from the groupconsisting of aluminum nitride, gallium nitride, silicon nitride,titanium nitride, silicon carbide, titanium carbide, titanium boride,titanium diboride, and aluminum boride comprises aluminum nitride. 8.The polycrystalline compact of claim 1, wherein the polycrystallinecompact is substantially free of metallic phases comprising cobalt,nickel, iron, and alloys thereof.
 9. A method of fabricating apolycrystalline compact, comprising: forming a mixture comprisingdiamond, non-cubic boron nitride, and a metal or semimetal, the metal orsemimetal selected from the group consisting of aluminum, gallium,silicon, and titanium; encapsulating the mixture in a container; andsubjecting the encapsulated mixture to a pressure of at least 5.0 GPaand a temperature of at least 1,100° C. for a period of time from about1 second to about 5 minutes to form a polycrystalline material from themixture, the polycrystalline material comprising the diamond, cubicboron nitride formed from the non-cubic boron nitride, and at least onehard material selected from the group consisting of aluminum nitride,gallium nitride, silicon nitride, titanium nitride, silicon carbide,titanium carbide, titanium boride, titanium diboride, and aluminumboride; wherein the diamond, the cubic boron nitride, and the hardmaterial are intermixed and interbonded within the polycrystallinematerial.
 10. The method of claim 9, wherein forming the mixturecomprising diamond, non-cubic boron nitride, and the metal or semimetalcomprises mixing the diamond with the non-cubic boron nitride andaluminum powder.
 11. The method of claim 9, wherein forming the mixturecomprising diamond, non-cubic boron nitride, and the metal or semimetalcomprises mixing diamond having an average particle size from about 50nm to about 40 μm with the metal or semimetal and the non-cubic boronnitride.
 12. The method of claim 9, wherein forming the mixturecomprising diamond, non-cubic boron nitride, and the metal or semimetalcomprises mixing non-cubic boron nitride having an average particle sizefrom about 1 μm to about 40 μm with the diamond and the metal orsemimetal.
 13. The method of claim 9, wherein subjecting theencapsulated mixture to the pressure of at least 5.0 GPa and thetemperature of at least 1,100° C. comprises subjecting the encapsulatedmixture to a pressure of at least about 7.5 GPa.
 14. The method of claim9, wherein subjecting the encapsulated mixture to the pressure of atleast 5.0 GPa and the temperature of at least 1,100° C. comprisessubjecting the encapsulated mixture to a temperature of at least about1,400° C.
 15. A polycrystalline compact, comprising: diamond; cubicboron nitride; and at least one hard material selected from the groupconsisting of aluminum nitride, gallium nitride, silicon nitride,titanium nitride, silicon carbide, titanium carbide, titanium boride,titanium diboride, and aluminum boride; wherein the diamond, the cubicboron nitride, and the hard material are intermixed and interbonded toform a polycrystalline material, and wherein the polycrystalline compactat least one of comprises from about 3 atomic percent to about 15 atomicpercent boron or has a density of at least about 3.30 g/cm³; and whereinthe polycrystalline compact has a Young's modulus of at least about 700GPa.
 16. An earth-boring tool, comprising: a bit body; and at least onepolycrystalline compact secured to the bit body, the polycrystallinecompact comprising: diamond; cubic boron nitride; and at least one hardmaterial selected from the group consisting of aluminum nitride, galliumnitride, silicon nitride, titanium nitride, silicon carbide, titaniumcarbide, titanium boride, titanium diboride, and aluminum boride;wherein the diamond, the cubic boron nitride, and the hard material areintermixed and interbonded to form a polycrystalline material, andwherein the at least one polycrystalline compact comprises a materialhaving a Young's modulus of at least about 700 GPa; and wherein thepolycrystalline compact at least one of comprises from about 3 atomicpercent to about 15 atomic percent boron or has a density of at leastabout 3.30 g/cm³.
 17. A method of fabricating a polycrystalline compact,comprising: forming a mixture comprising diamond, non-cubic boronnitride, and a metal or semimetal, the metal or semimetal selected fromthe group consisting of aluminum, gallium, silicon, and titanium;encapsulating the mixture in a container; and subjecting theencapsulated mixture to a pressure of at least 5.0 GPa and a temperatureof at least 1,100° C. to convert at least a portion of the non-cubicboron nitride from a wurtzitic phase to a cubic phase and form apolycrystalline material from the mixture, the polycrystalline materialcomprising the diamond, the wurtzitic phase boron nitride, and at leastone hard material selected from the group consisting of aluminumnitride, gallium nitride, silicon nitride, titanium nitride, siliconcarbide, titanium carbide, titanium boride, titanium diboride, andaluminum boride; wherein the diamond, the wurtzitic phase boron nitride,and the hard material are intermixed and interbonded within thepolycrystalline material.
 18. A method of fabricating a polycrystallinecompact, comprising: forming a mixture comprising diamond, non-cubicboron nitride, and metal or semimetal particles having an averageparticle size from about 50 nm to about 1μm, the metal or semimetalselected from the group consisting of aluminum, gallium, silicon, andtitanium; encapsulating the mixture in a container; and subjecting theencapsulated mixture to a pressure of at least 5.0 GPa and a temperatureof at least 1,100° C. to form a polycrystalline material from themixture, the polycrystalline material comprising the diamond, cubicboron nitride formed from the non-cubic boron nitride, and at least onehard material selected from the group consisting of aluminum nitride,gallium nitride, silicon nitride, titanium nitride, silicon carbide,titanium carbide, titanium boride, titanium diboride, and aluminumboride; wherein the diamond, the cubic boron nitride, and the hardmaterial are intermixed and interbonded within the polycrystallinematerial.